CN105089744A - 排气后处理系统及用于排气后处理的方法 - Google Patents

排气后处理系统及用于排气后处理的方法 Download PDF

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CN105089744A
CN105089744A CN201510259015.4A CN201510259015A CN105089744A CN 105089744 A CN105089744 A CN 105089744A CN 201510259015 A CN201510259015 A CN 201510259015A CN 105089744 A CN105089744 A CN 105089744A
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exhaust
treatment system
separator
catalytic converter
oxidation catalytic
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P·托舍夫
A·德林
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MAN Energy Solutions SE
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MAN Diesel and Turbo SE
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Abstract

用于内燃机的排气后处理系统(2)，其具有布置在内燃机(1)下游用于化学吸附硫氧化物的包含含钙颗粒的分离器(4)，以及布置在内燃机(1)下游和分离器(4)上游的用于将SO2氧化为SO3的氧化催化转化器(3)。

Description

排气后处理系统及用于排气后处理的方法
技术领域
本发明涉及排气后处理系统。本发明还涉及用于排气后处理的方法。
背景技术
在固定式内燃机(例如用于发电厂的固定式内燃机)的燃烧过程中，以及在非固定式内燃机(例如用于轮船的非固定式内燃机)的燃烧过程中，产生硫氧化物如SO2和SO3，其中这些硫氧化物通常形成于含硫化石燃料(如煤、矿煤、褐煤、石油或重质燃料油)的燃烧期间。因此，这种内燃机被分配有排气后处理系统，该系统特别用于离开内燃机的排气的脱硫。
对于排气脱硫，从现有技术主要已知的是吸附法，所述吸附法主要利用生石灰(CaO)或消石灰(Ca(OH)2)或碳酸钙(CaCO3)作为吸附剂。在此过程中，形成粉尘或颗粒，其中为了从排气中除去硫酸钙粉尘，必须在脱硫下游使用过滤装置。
从DE3603365C2中已知用于处理包含氮氧化物和粉尘的排气的方法以及排气后处理系统。
此外，所谓的洗涤器也被用于脱硫，其中借助于水将SO2从排气中除去。随后，包含在洗涤水中的二氧化硫借助于碱(举例来说，例如NaOH)而被中和。在此中和之前，在大多数情况下另外地将洗涤出的SO2氧化为SO3，因为这确保更好的分离并允许使用钙化合物，这使得SO3形成CaSO4并由此可以沉淀。这通常通过向集污槽中鼓气来实现(US4515754A1)。
发明内容
由此着手，本发明的目的是基于创建一种新型排气后处理系统和一种新型排气后处理方法。
这一目的通过根据权利要求1的排气后处理系统来实现。根据本发明的用于内燃机的排气后处理系统包括布置在内燃机下游用于化学吸附硫氧化物的具有含钙颗粒的分离器，以及布置在内燃机的下游和分离器的上游用于将SO2氧化为SO3的氧化催化转化器。通过利用所述分离器，有可能省略用于将硫酸钙或硫酸钠粉尘从排气中除去的过滤装置。二氧化硫与分离器的含钙或含钠或含镁颗粒反应并可经由所述颗粒排出。将SO2氧化为SO3的氧化催化转化器的使用使得排气在分离器中的短停留时间成为可能，因为SO3与分离器的含钙或含钠或含镁颗粒的反应比SO2更快。根据本发明的排气后处理系统使得排气的有效脱硫成为可能。
根据有利的进一步发展，分离器中的颗粒包括CaO和/或Ca(OH)2和/或CaCO3和/或Na2CO3和/或MgO，其中所述颗粒的粒度在1mm至8mm之间。在此，所述分离器被特别设计为带有移动床或流化床的错流分离器。这使得排气的特别有效的脱硫成为可能。
根据有利的进一步发展，将一个加热装置布置在氧化催化转化器的上游，该装置将排气加热至大于350℃，优选大于400℃，特别优选大于450℃的温度。这使得可以特别有效地将SO2氧化为SO3并因此使排气有效脱硫。
对于排气增压内燃机，氧化催化转化器位于排气涡轮增压器的涡轮的上游，其中分离器位于排气涡轮增压器的涡轮的下游。通过存在于涡轮上游的相对高的温度和压力，有助于在氧化催化转化器中将SO2氧化为SO3。
根据更有利的进一步发展，排气后处理系统包括将NH3-前体物质(尿素)或气态NH3引入到排气中的装置，所述装置布置在氧化催化转化器的下游。因此可进一步改善排气的脱硫。
根据本发明的排气后处理方法限定于权利要求14中。
附图说明
由从属权利要求(subclaim)和以下说明书获得本发明的优选的进一步发展。借助于附图，更详细地解释本发明的示例性实施方案，而非限制于此。其显示为：
图1：根据本发明的第一排气后处理系统的框图；
图2：根据本发明的第二排气后处理系统的框图；
图3：根据本发明的第三排气后处理系统的框图；以及
图4：根据本发明的第四排气后处理系统的框图。
具体实施方式
本发明涉及用于内燃机的排气后处理系统，例如用于发电厂中的固定式内燃机或用于轮船上的非固定式内燃机。所述排气后处理系统特别地用于使用重质燃料油运行的船用柴油机上。
图1示出了位于内燃机1下游的排气后处理系统2的第一示例性实施方案，其中排气后处理系统2包括布置在内燃机1下游的氧化催化转化器3。在氧化催化转化器3中，根据以下反应方程式，SO2反应成为SO3
2SO2+O2→2SO3
在用于将SO2氧化为SO3的氧化催化转化器3中将以下化学元素用作活性组分：V(钒)和/或K(钾)和/或Na(钠)和/或Fe(铁)和/或Ce(铈)和/或Cs(铯)和/或这些元素的氧化物。
组分钒(V)的量计为大于5％，优选大于7％，特别优选大于9％。
氧化催化转化器3使用TiO2(二氧化钛)和/或SiO2(二氧化硅)作为基材，优选通过WO3(氧化钨)来稳定。
此外，根据本发明的排气后处理系统2包括布置在氧化催化转化器3下游的包含含钙或含钠或含镁颗粒的分离器4，该分离器4优选为移动床反应器或流化床反应器。
含钙或含钠或含镁的颗粒优选包括CaO和/或Ca(OH)2和/或CaCO3和/或Na2CO3或NaHCO3，MgO。在此，硫氧化物与含钙颗粒根据以下反应方程式反应，即对于Ca(OH)2根据以下反应方程式
Ca(OH)2+SO2←→CaSO3+H2O
Ca(OH)2+SO2+1/2O2←→CaSO4+H2O
Ca(OH)2+CO2←→CaCO3+H2O
Ca(OH)2+SO3←→CaSO4+H2O
以及对于CaCO3根据以下反应方程式
CaCO3+SO2←→CaSO3+CO2
CaCO3+SO2+1/2O2←→CaSO4+CO2
CaCO3+SO3←→CaSO4+CO2
以及对于Na2CO3和NaHCO3根据以下反应方程式
Na2CO3+SO2←→Na2SO3+CO2
Na2CO3+SO3←→Na2SO4+CO2
2NaHCO3+SO3←→Na2SO4+2CO2+H2O
以及对于MgO根据以下反应方程式
MgO+SO2+1/2O2←→MgSO4
在此根据本发明，显然SO3与含钙或含钠或含镁颗粒的反应比SO2更快，这就是为什么用于将SO2氧化为SO3的氧化催化转化器3被布置在内燃机1的下游和分离器4的上游。因为这一点，可以提高脱硫的效率。
优选地，SO2氧化为SO3以如此方式在氧化催化转化器3中进行：在氧化催化转化器3的下游，排气中所有硫氧化物(SOX)中的SO3组分计为至少20％，优选大于40％，特别优选大于60％。
在分离器4中，硫氧化物与颗粒反应形成硫酸钙或硫酸钠或硫酸镁，所述硫酸钙或硫酸钠或硫酸镁可以与分离器4的颗粒一起被排出。
分离器4中的颗粒的粒度为在1mm至8mm之间，优选在4mm至8mm之间。由于该颗粒的粒度相对较大，此外所述颗粒并不与硫氧化物反应直至中心，而是包含在至少部分地还未与硫氧化物反应的组分的核中，然后该核被硫酸钙的壳所包围。
优选地给分离器4配备一个装置以将颗粒与在移动床或流化床中经由颗粒截留的硫酸钙分离，所述硫酸钙与颗粒一起从移动床反应器或流化床反应器中排出。该装置可以为例如滚筒剥皮机(drumpeeler)、转筒筛或碾磨机。不含硫酸钙的颗粒可以随后返回至分离器4中以便由此形成颗粒回路和更有效地利用所述颗粒。
图2示出了本发明的一种变体，其中内燃机1显示为排气增压内燃机，其中排气后处理系统2相应地包括排气涡轮增压器的涡轮5，其中使离开内燃机1的排气膨胀以提取机械能。在此类排气增压内燃机的情况下，从排气的流动方向来看，氧化催化转化器3布置在涡轮5的上游，其中分离器4布置在涡轮5的下游。存在于涡轮5上游的排气流中的高压和高温有助于在氧化催化转化器3中将SO2氧化为SO3。
根据本发明用于内燃机的排气后处理系统2的又一示例性实施方案如图3所示，其中图3的排气后处理系统2正如图1的排气后处理系统2，包括氧化催化转化器3和分离器4。此外，图3的排气后处理系统2包括布置在氧化催化转化器3上游的加热装置6，该加热装置6将氧化催化转化器3上游的排气加热至大于350℃，优选大于400℃，特别优选大于450℃的温度。这有助于在氧化催化转化器3中将SO2氧化为SO3。
根据本发明用于内燃机的排气后处理系统2的又一示例性实施方案如图4所示，其中图4的排气后处理系统2正如图2的排气后处理系统2，包括氧化催化转化器3、涡轮5、分离器4和另外地用于将气态NH3引入到排气中的装置7，其中这一将气态NH3引入到排气中的装置7布置在氧化催化转化器3的下游，如此相应地将NH3引入到氧化催化转化器3下游的内燃机1的排气中。在此过程中，可以提供或者将NH3直接以气态形式引入到排气流中，或者将NH3-前体物质，举例来说，例如尿素注入排气流中并在排气流中蒸发为NH3。将气态NH3引入到氧化催化转化器3下游的排气流中具有优势——因为这一点，可以由此改善随后的脱硫。
对于如图1-4所示的排气后处理系统2，可以使用优选设计为移动床反应器或流化床反应器的多级分离器4，以便改善硫酸钙或硫酸钠或硫酸镁的分离，其中特别当使用多级分离器4时，不同粒度的颗粒被用于分离器4的单独的级中。
优选地，使用设计为错流分离器的分离器4。
通过根据本发明的排气后处理方法，根据本发明的排气后处理系统2允许对排气进行有效脱硫。对于借助于根据本发明的排气后处理系统2的排气脱硫，首先经由氧化催化转化器3传导离开内燃机的排气，以便可以将SO2氧化为SO3。随后经由包含含钙颗粒的分离器4传导所述排气。如前所述，通过将NH3引入到排气中可以改善排气的脱硫。通过提供或使用高排气温度可以改善SO2到SO3的氧化。参考关于图1-4的解释。
除了使用颗粒，借助于排气洗涤器的分离也是有利的，所述洗涤器布置在用于SO2-氧化的催化转化器的下游。因为这一点，一方面，由于SO3比SO2明显更易溶于水中，所以提高了排气洗涤器中的分离率，由此可以改善分离性能和/或减小洗涤器尺寸。此外，可以省略如US4515754A1中所述的向用于SO2-氧化的集污槽中鼓气。
参考编号列表
1.内燃机
2.排气后处理系统
3.氧化催化转化器
4.分离器
5.涡轮
6.加热装置
7.装置

Claims (15)

1.用于内燃机的排气后处理系统(2)，具有布置在内燃机(1)下游的排气洗涤器，或用于化学吸附硫氧化物的包含含钙和/或含钠和/或含镁颗粒的分离器(4)，以及布置在内燃机(1)下游和分离器(4)上游的用于将SO2氧化为SO3的氧化催化转化器(3)。
2.根据权利要求1的排气后处理系统，其特征在于所述分离器(4)中的颗粒包括CaO和/或Ca(OH)2和/或CaCO3和/或Na2CO3和/或NaHCO3。
3.根据权利要求1或2的排气后处理系统，其特征在于所述颗粒的粒度在1mm至8mm之间。
4.根据权利要求1至3任一项的排气后处理系统，其特征在于所述分离器(4)被设计为移动床反应器或流化床反应器。
5.根据权利要求1至4任一项的排气后处理系统，其特征在于所述分离器(4)被设计为错流分离器。
6.根据权利要求1至5任一项的排气后处理系统，其特征在于所述分离器(4)被设计为多级分离器，其中所述分离器(4)的单独的级中的颗粒粒度彼此不同。
7.根据权利要求1至6任一项的排气后处理系统，其特征在于用于将SO2氧化为SO3的氧化催化转化器(3)包含钒和/或钾和/或钠和/或铁和/或铈和/或铯和/或这些元素的氧化物作为活性组分，其中所述氧化催化转化器使用二氧化钛和/或二氧化硅作为基材，优选通过氧化钨来稳定。
8.根据权利要求1至7任一项的排气后处理系统，其特征在于所述氧化催化转化器(3)包含钒作为活性组分，所述钒组分大于5％，优选大于7％，特别优选大于9％。
9.根据权利要求1至8任一项的排气后处理系统，其特征在于对于排气增压内燃机，所述氧化催化转化器(3)位于排气涡轮增压器的涡轮(5)的上游，其中分离器(4)位于涡轮增压器的涡轮(5)的下游。
10.根据权利要求1至9任一项的排气后处理系统，其特征在于在所述氧化催化转化器(3)的上游布置有加热装置(6)，所述加热装置(6)将排气加热至大于350℃，优选大于400℃，特别优选大于450℃的温度。
11.根据权利要求1至10任一项的排气后处理系统，其特征在于用于将气态NH3引入到排气流中的装置(7)，所述装置(7)布置于氧化催化转化器(3)的下游。
12.根据权利要求1至11任一项的排气后处理系统，其特征在于SO2-氧化催化转化器下游的SO3/SOx比计为至少0.4，优选为至少0.5，最优选为至少0.6。
13.根据权利要求1至12任一项的排气后处理系统，其特征在于所述颗粒的硫酸盐层被除去，且所述颗粒返回至分离器上游和/或分离器中。
14.对于离开内燃机的排气的排气后处理方法，其中经由用于将SO2氧化为SO3的氧化催化转化器(3)并随后经由用于化学吸附硫氧化物的包含含钙颗粒的分离器(4)来传导所述排气。
15.根据权利要求14的方法，其特征在于所述方法借助于根据权利要求1至13任一项的排气后处理系统来进行。
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